Trifluoromethylbenzyl thiolcarbamates as herbicides

ABSTRACT

SUBSTITUTED BENZYL THIOLCARBAMATES CONTAINING FLUORINE ARE DESCRIBED WHICH ARE USEFUL FOR CONTROLLING PERENNIAL AND ANNUAL GRASSES.

United States Patent 3,687,653 TRIFLUOROMETHYLBENZYL THIOLCARBA- MATES AS HERBICIDES Frederic G. Bollinger, Copley, and John J. DAmico,

Akron, Ohio, assignors to Monsanto Company, St. Louis, Mo. No Drawing. Filed Apr. 13, 1970, Ser. No. 28,000

Int. Cl. A01n 9/22 US. Cl. 71-94 19 Claims ABSTRACT OF THE DISCLOSURE Substituted benzyl thiolcarbamates containing fluorine are described which are useful for controlling perennial and annual grasses.

The invention relates to iluorobenzyl thiolcarbamates, to methods of destroying or controlling undesired vegetation and to herbicidal compositions.

BACKGROUND OF THE INVENTION Specific benzyl thiocarbamate herbicides containing fluorine in the benzyl radical have not heretofore been described although Harman and one of us has described a method of destroying or controlling undesired vegetation by applying a toxic concentration of a halogen substituted benzyl ester of a thiocarbamic acid which halogen is preferably chlorine but bromine and to a lesser extent fluorine and iodine are also suitable. Harman and DAmico U .8. 2,992,091, July 11, 1961. Formative action on broad leaf plants like that commonly associated with chlorophenoxyacetic acids and toxicity to a variety of annual grasses are described. Severe formative action on broad leaf plants is exerted by certain polyh-alogenated benzyl thiocarbamates. However, there is a need for improved toxicants which can be used in areas of broad leaf crops, for example sugar beets, without exerting formative action, at rates effective for weed control and which control perennial grasses as well as annual grasses. The present invention is concerned with such improvements in the field of halobenzyl thiocarbamate herbicides.

The new compounds of this invention are monofiuorobenzyl and mono(trifluoromethyl)benzyl thiolcarbamates wherein the amino radical is di(lower alkyl)amino of 1-4 carbon atoms in each alkyl group, diallylamino, N-allyl N-lower alkyl amino, piperidino, dimethylpiperidino, 1- pyrrolidinyl or dimethyl-l-pyrrolidinyl. These compounds exert a high degree of toxicity to quac-kgrass and certain other perennial grasses at low rates of application at which rates there is usually little or no effect on wheat, soybeans, sugar beets, and corn. It is preferred that the amino substituent is di-lower alkyl amino of 2 or 3 carbon atoms in each alkyl group. When piperidino is the amino substituent, it is preferred that the benzyl substituent is ortho or meta fluorobenzyl and when 1pyrrolidinyl is the amino substituent it is preferred that the benzyl substituent is ortho or para fluorobenzyl. Illustrative compounds are 2, 3 and 4-(alpha,alpha,alpha-trifluoromethylbenzyl)- diisopropylthiolcarbamates, 2, 3 and 4-(alpha,al-pha,alpha-trifiuoromthylbenzyD- diethylthiolcarbamates,

2, 3 and 4-a'lpha,alpha,alpha-trifluoromethylbenzyD- di-n-propylthiolcarbamates,

2, 3 and 4-fiuorobenzyl diallylthiolcarbamates,

2, 3 and 4-p-fluorobenzyl N-allyl-N-isopropylthiolcarbamates,

3-(alpha,alpha,alpha-trifiuoromethylbenzyl) dimethyl- .thiolcarbamate,

2, 3 and 4-fluorobenzyldimethylthiolcarbamates,

Patented Aug. 29, 1972 The fluoro substituted benzyl esters of this invention are prepared by condensing the corresponding benzyl halide with a salt, preferably alkali metal salt, or amine salt of the appropriate thiolcarbamic acid in aqueous or organic solvent medium. A salt of the thiolcarbamic acid is conveniently prepared by reacting carbonyl sulfide with the appropriate amine in known manner. The fiuoro substituted benzyl halide is then reacted with the salt to form the desired ester. Suitable variation of the foregoing procedure is the addition of carbonyl sulfide to an alkaline mixture containing the amine .and fiuoro substituted benzyl halide. Alternatively the appropriate chlorothiocarbonate where R is the desired fluoro substituted benzyl radical is reacted wtih the amine. The iluoro substituted benzyl thiolcarbamates, so produced, may be purified by distillation if desired and in the case of solid products by crystallization. The products are sufficiently pure for most purposes after stripping the solvent and other volatile constituents. It is preferred to strip by heating at 110-150 C. at 1-2 mm./Hg pressure to assure removal of any residual fluorobenzylhalide.

The condensation of 3-(alpha,alpha,alpha-trifluoromethyl)benzyl chloride with sodium 2,5-dimethyl-1-pyrrolidinecarbothiolate is performed as follows: To a solution comprising 14 grams (0.14 mole) of 2,5-dimethyl-1- pyrrolidine, 1 6 grams (0.1 mole) of 25% sodium hydroxide and 50 ml. of water at 0-10 C. is added 7.8 grams (0.11 mole) of carbonyl sulfide in 10 minutes. There is then added in one portion 19.5 grams (0.1 mole) of 3-(alpha,alpha,=alpha trifluoromethyDbenzyl chloride and the reaction mixture is stirred at the indicated times and temperatures: first hour 05 C.; second hour 510 C.; third hour IO-15 C.; fourth hour 15-20 C.; fifth hour 2025 C. and 18 hours at 25-30 C., after which 200 m1. of water and 500 ml. of ethyl ether are added and the mixture stirred 15 minutes. The water layer is separated and discarded. The ether layer containing the product is washed with water until the washings are neutral and then dried over Na SO The ether and any unreacted 3 (alpha,alpha,alpha trifiuoromethyDbenzyl chloride is removed by distillation in vacuo by heating to 140-150 C. at 1-2 mm. The' 3-(alpha,alpha,alpha-trifluoromethyDbenzyl 2,5-dirnethyl-l-pyrrolidinecarbothiolate is a liquid obtained in yield.

3 (alpha,alpha,alpha trifluoromethyl)benyl diisopropylthiolcarbamate is prepared as follows: There is added 25 grams (0.35 mole) of 85% carbonyl sulfide in 45 minutes to an aqueous solution at 0-10 C. comprising 45 grams (0.45 mole) diisopropylamine, 48 grams (0.3 mole) 25% sodium hydroxide and 100 ml. of water followed by the addition in one portion of 58 grams (0.3 mole) of 3 (alpha,alpha,alpha-trifiuoromethyl) benzyl chloride. The mixture is stirred for one hour at 010 C. and then -is allowed to warm slowly to room temperature and stirred overnight after which 500 ml. of water and 300 ml. of ethyl ether are added. The mixture is stirred one hour, the organic-water layers are separated and the water layer is extracted with an additional 100 ml. of ethyl ether and then discarded. The ether extract is combined with the previously separated organic layer and the combined ether solution is Washed with water until the washings are neutral, dried over Na SO and filtered through clay. The ether is removed by heating in vacuo up to 80-90 C. at 1-2 mm. on a steam bath. The residue is 83 grams (87% yield) of a yellow oil which is distilled to give 3 (alpha,alpha,alpha trifluoromethyDbenzyl di- 4. of the pan, then a known number of seeds of velvetleaf, morningglory, lambsquarter, smartweed, Bromus tectorum, and barnyardgrass scattered across the pan. After the seeds are planted and pressed down with the tamper isopropylthiolcarbamate as a colorless oil boiling at 120- 5 the pans are set aside until the time of chemical treatment 125 C. at 0.2 mm. Hg, N 1.4959. Analysis gives and just prior to treatment a counted number of quack- 4.21% N, 10.10% S, and 18.48% F compared to 4.39% grass rhizomes 3-4 in. long, Iohnsongrass propagules and N, 10.04% S, and 17.85% F calculated for C H F NOS. segments of Canada thistle roots 3-4 in. long are placed In a similar manner, other fluoro substituted benzyl in the pan, the plants covered with 450 grams of soil esters are prepared by selection of the proper amine and 10 containing the chemical to be tested. Two or more pans substituted benzyl halide. Representative esters are obsimilarly planted are covered with untreated soil as contained, and their properties are shown in Table I. The trols. The treated and untreated pans are moved into the compounds are insoluble in water and soluble in ether, greenhouse where they are watered from below as needed. acetone, chloroform, benzene, heptane and ethyl acetate. Approximately two weeks after application of the test TABLE I Analysis, percent Calculated Found Yield, M.P., Compound percent N S F N S F G. B.P., C.

3-(a,a,m-trifluoromethyl)benzyl l-pyrrolidinecarbothiolate 62 11.08 11.39 i'quid. 4-fiuorobenzyl diisopropylthiolcarbamate 95 5. 20 11.90 7.05 5.00 11.76 7.18 39-3915 ur ing 1.2

' .5 B-fiuorobenzyl diisopropylthiolcarbamate l 99 5. 20 11. 90 7.05 5. 27 11. 78 7. 19 9 72-73 D 2-rluor0benzyl diisopropylthiolcarbamate- 3 91 5. 20 11.90 7.05 5.31 11.81 7. 17 2 52-52. 5 3-fiuorobenzyl diethylthiolcarbamate 95 Amber liquid. 4-fluorobeuzyl l-piperidinecarbothiolate. 99 D0. 3-fluorobenzy1 l-piperidiuecarbothiolate 4 87 Do. 3-(a, a, a-trifluoromethynbenzyl l-piperidinecarb othiol 4 76 Do. 2-fiuorobenzyl l-piperidineearbot-hiolate 3 92 d-fiuorobenzyl diethylthiolcarbamatm 99 D0. Q-fiuorobenzyl diethylthiolcarbamatm 87 Do. 2-fiuorobenzyl 1pyrro1idinecarbothio1ate 100 Do. 3-fluorobenzyl l-pyrrolidineearbothiolate Do. 4-fluorobenzyl 2,5-d.imethyl-1-pyrrolidinecarbot 10a 100 Do. 2-fiuorobenzyl 2,B-dimethyl-l-pyrrolidinecarbothiolate- 100 D0. 3-fluorobenzyl 2,5-dimethyl-Lpyrrolidinecarbothiolate. 100 Do. -fiuorobenzyl l-pyrrolidinecarbothiolate 3-(a,a,a-trifiuoromethyl)benzyl 2,6Fdimethyl-1- 4 82 D0.

piperidinecarbothiolate. 3-(a,a,a trifluoromethyl)benzyl N allyl N- 98 4. 41 10. 10 17. 96 4. 10. 15 18. 1264301015.

propylthiolcarbamate. 3-(q a trifluoromethyl)benzyl diethylthiolcarbamate 89. 5 4. 81 11. 01 19. 57 4. 84 11. 17 19. 59 13%135/1 1.5023

D 3-(m,a,a-trifiuoromethyl)benzyl dimethylthiolcarbamate 89. 6 5. 31 12. 17 21. 65 5. 32 12. 34 22. 04 sags/0.1 51

D 5 O6. 3-(,,a-trifiuoromethyl)benzyl dibutylthiolcarbamate 95. 5 4. 03 9. 23 16. 3. 79 9. l8 16. 53 1310141 510424 D 9 2. 3 (a,a,a-trifiuoromethyl)benzyl di-n-propylthiolcarbamate 10D 4. 39 10. 04 17. 85 4. 10. 10 18. 29 15111 12 29 20 n 968. 3 (a,a,a-trifiuoromethy1)benzyl diisobutylthiolcarbamate 100 4.03 9. 22 16.40 4. 21 9. 45 16 82 15;;1230111) 14 D 5 1. 9 4-fluorobenzyl diisobutylthiolcarbamate 95 4. 10. 77 6.39 4.80 10. 81 6. 54 lag-15,140.15

1 Ether removed in vacuo at 30 C. at 1-2 mm. and solid air-dried at 25.30 C.

3 Recrystallized from heptane.

3 No ether used, added 500 ml. H 0, stirred at 0.10 G. for one hour, filtered and air-dried at; 2530 C.

4 Stripped at 170 C. at 12 mm.

Pre-emergence tests are carried out employing viable seeds or vegetative propagules of representative plants which include narrowleaf perennials. The plant spectrum is as follows:

Vegetative propagules of Canada thistle, Iohnsongrass and quackgrass are used, and the other species are planted 7 as seeds.

An aluminum pan is level filled with soil and compacted to a depth of approximately in. from the top by means of a template tamper. A known number of nutsedge nutlets and cocklebur are planted lengthwise chemical the results are observed and recorded. The number of plants of each species which germinated and grew are counted and converted to a herbicidal rating by means of a fixed scale based on average percent germina tion. The numbers of plants emerging are converted directly to herbicide ratings according to the fixed scale by comparison to the number of plants emerging from the seeds and propagules planted in the untreated control pans. Thus, based upon the number of plants Which emerged from the untreated control the percentage of that number which emerged from similarly planted but chemically treated pans afiords a measure of the herbicidal Phytotoxicity ratings of representative fluorobenzyl thiolcarbamates which controlled quackgrass at 1 lb. per acre are recorded in Table II.

Application rate Canada Compound thistle bur 4-fiuorobenzyl diisopropylthiolcarbamate 3-fluorobenzyl diisopropylthiolcarbama 2-fluorobenzyl diisopropylthiolcarbamate S-fiuorobenzyl diethylthiolcarbamate- 4-fiuorobenzyl diethylthiolcarbamate. 2-fluorobenzyl diethylthiolcarbamate 2-fluorobenzyl 2,5-djmethyl-1- pyrrolidinecarbothiolate 3-(a,a,a-trifluoromethybbcowl-2,6-

dimethyl-l-piperidiuecarbothiolate- 3-(a,a,a-trifluoromethyl)benzyl diisopropylthlolearbamate O o 00F 0 o Cockle- Velvetleaf Motown-O00 B arnyardgrass Morningglory Johnson grass Bromus tecforum Smart- Nutweed sedge Lambsgrass M c POOP H o o H H Homo o H c u no "HP-IN H N o: rec-new w o:

0: ea e: Queue: e: co

0 co H -v-oo o c H s: w Hume: to co to ee ammo: w ea Comparison of unit activity on quackgrass and safety to crops at the effective rate is illustrated by results in Table 111. Aluminum pans approximately 9 in. x in. x 2 /2 in. with holes in the bottoms are filled with Ray silt loam leveled and compressed until the soil is about in. below the top of the pans. Each pan is planted with six 4 inch sections of quackgrass rhizomes having at least four nodes each, 5 soybean seeds, 12 wheat seeds and alfalfa seed in a thickly planted row. The test chemicals are applied to 450 grams of soil contained in the same size aluminum pans without holes at various dosages ranging from lb. per acre to 1 pound per acre or higher. Each chemical is applied at a dilution of gallons per acre in the form of 1:1 acetone/water solution with a belt sprayer. The treated soil is mixed thoroughly after spraying to assure uniform distribution of the test chemical throughout the soil and used to cover the propagules and seeds. All pans receive 0.3 inch of overhead irrigation from a rain simulator.

Three difierent plantings treated with each test chemical are placed at different locations in the greenhouse and the results of the three tests averaged. Observations for percent weed inhibition and percent crop injury based on a scale of 0 to 100 where 0 represents no inhibition of weed top growth or crop injury and 100 represents complete weed inhibition or crop injury are made three weeks after treatment. Soil moisture is maintained by sub-irriga tion. The minimum dosage at which a commercially acceptable level of quackgrass control is obtained together with the effect on crop plants are recorded in Table III.

TABLE IIL-CROP SELECTIVIT benzyl thiolcarbamates are applied by pre-emergence application to the surface of the cover soil of pans planted with major narrowleaf weeds and the minimum rate for weed control observed from evaluation of tests over a range of dosages. Johnsongrass seeds are used in this case.

Somewhat higher dosages are required for control of Bromus tectorum and of nutsedge by surface application than by incorporation into the cover soil. Selective control of crabgrass, sedges and barnyardgrass in rice is attained by surface application in the manner described above of 4 fluorobenzyl diisopropylthiolcarbamate. At four pounds per acre, substantially no injury to rice is observed whereas nutsedge is controlled at two pounds [Percent inhibition after three weeks-average for three plantings] Rate, Quack- Y- Compounds #/a. grass Wheat bean Alfalfa Corn 1 3-(a,a,a-trifluoromethyl)benzyl diisopropylthiolcarbamate 1 95 0 0 3 0 4-fiuorobenzy1 diisopropylthiolcarbamate 98 0 7 l0 0 3 fluorobenzyl diisopropylthiolearbamate. 97 0 0 7 5 2-fluor0benzyl diisopropylthiolcarbamate 83 0 10 10 10 3-fluorobenzyl diethylthiolcarbamate. $4 83 0 7 0 8 4-fluorobenzyl diethylthiolcarbamate 100 0 10 0 5 2-fluorobenzyl diethylthiolcarbamate 97 3 7 0 5 1 Corn tested at /6, lb./a. observed four weeks after planting.

Similar unit activity tests are carried out against yellow nutsedge (Cyperus esculentus). Ten tubers are planted in the above-described pans and the test chemical incorporated into the cover soil. Control of yellow nutsedge at /2 lb./acre is observed with either 0, m or p-fiuorobenzyl N,N-diisopropylthiolcarbamate. The percent inhibition at this dosage, average of 3 tests, is 98%, 91% and 91% respectively.

Other unit activity tests are carried out and the results observed 20 days after planting. Representative fluoroupon observation made about three weeks after planting.

TABLE V.SUGAR BEET CULTURE Maximum Minimum control Safe rate, rate, lbs./acre lbsJacre Barn- Sugar yard Wild Bromua Blank Compound beet Wheat Grass oat tectorum grass B-fluorobenzyl diethylt-hiolcarbamate 2 1 56 A. K 4-fiuorobenzyl diethylthiolcarbamate 4 2 M 2-fluorobenzyl diethylthiolcarbamate 2 1 1 4 B-fluorohenzyl N ,N-diisopropylthiolearbamate 4 l/ y; 36 4-fluorobenzyl N, N-diisopropylthiolearbamate 4 }6 M 3-(alpha, a1pha,alpha-triflnoromethyl) benzyldnsopropylthiolcarbamate 4 1 2 1 5% The fiuorobenzyl thiolcarbamates are insoluble in water but soluble in common organic solvents. They may be dispersed directly in water or a solution in an organic solvent emulsified in aqueous medium by the aid of a dispersing agent. The usual mode of application is in the form of a spray containing the active ingredient in a concentration within the range of 0.01-% by weight at a dosage within the range of /1 to 5 pounds per acre. Emulsifiable concentrates may be prepared which are diluted with water and applied to soil surface or incorporated into the top soil layer.

As dispersing and wetting agents there may be employed soft or hard sodium or potassium soaps, alkylated aromatic sodium sulfonates such as sodium dodecylbenzene sulfonate, amine salts as for example, dibutylarnmonium dodecylbenzenesulfonate, alkali metal salts of sulfated fatty alcohols, ethylene oxide condensation products of alkyl phenols and other dispersing and wetting agents and mixtures thereof. Formulation of dry compositions is accomplished by mixing with finely divided solid carriers. Suitable carriers comprise talc, clay, pyrophyllite, silica and fullers earth. A dry formulation may be applied as a dust or dispersed in aqueous medium. It the latter is intended the addition of a Wetting or dis persing agent is advantageous.

In general, herbicidal compositions are formulated with the aforesaid toxicants as essential active ingredients in minor or major proportion together with herbicidal adjuvant as carrier in accordance with the table below. Surface active agent is usually present except in the case of granules.

Concentration of Type of formulation: active ingredient, percent (1) Granules of relatively large particle (6) One of the less common types of formulations depending on the desired mode of application .0l-95 The compounds may, if desired, be used in combination with other agricultural chemicals such as fertilizers, insecticides, fungicides, nematocides and other herbicides. Two or more herbicides may be combined to obtain specificity for diiferent species of undesired plants and to obtain mutually activating efiects. Examples of other herbicides which may be used in combination are N (1,1 dimethylpropynyl)-3,S-dichlorobenzamide, 5- amino-4-chloro-2-phenyl-3(2H)-pyridazinone; 4-(methylsulfonyl)-2,6-dinitro-N,N-dipropylaniline; alkyl thiolcarbamates, for example ethyl N-cyclohexyl N-ethylthiolcarbamate, propyl N ethyl N-n-butylthiolcarbamate, mono-, diand tri-chloroallyl diisopropylthiolcarbamate; triazines, for examples, 2-t-butylamino-4-methylamino-6- methylthio-s-triazine, 2 chloro-4-ethylamino-6-isopropylamino-s-triazine, 2. t-butylamino-4-ethylamino-6-methylthio-s-triazine, 2 (4 chloro-6-ethylamino-s-triazin-2-ylamino)-2-methylpropionitrile, 2 chloro-4,6-bis(isopropylamino)-s-triazine; the chloroacetanilides, for example, 2',6'-diethyl-N-methoxymethyl-2-chloroacetanilide, N-isopropyl-Z-chloroacetanilide; a,a,oc-trifluoro-2,6-dinitro-N,N- dipropyl-p-toluidine; ureas, for example 3-(3,4-dichlorophenyl)-1-methoxy-l-methylurea, 3 (4-bromo-3-chlorophenyl)-1-methoxy-1-methylurea, and 3 (3,4-dichlorophenyl)-1,1-dimethylurea.

The preferred method of application is to apply the toxicant prior to planting the crop and incorporate it into the top soil. Useful results are also obtained by applying to the soil surface after planting either before the crop emerges or in the case of cultivated crops as a band along the rows. The use in bands or strips may be either a preplant or a post-plant application. In addition to use in field crop culture the new compounds are also useful for the control of weedy grasses in greenhouses.

Post-emergence chemicals can be applied later, if desired, for example the carbamates, 3-(methoxycarbonylaminophenyl) -N (3 methylphenyl) carbamate or 4- chloro-2-butynyl-N-3-chlorophenylcarbamate.

Although the invention has been illustrated by typical examples, it is not limited thereto. Changes and modifications of the examples of the invention herein chosen for purposes of disclosure can be made which do not constitute departure from the spirit and scope of the invention.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. The method of controlling undesired vegetation which comprises applying to the soil medium a toxic concentration of a compound of the formula where R is trifluoromethyl, X and Y individually are lower alkyl or allyl or taken together with the nitrogen are 1- pyrrolidinyl, dimethyl-l-pyrrolidinyl, l-piperidinyl or dimethyl-l-piperidinyl.

2. The method of controlling quackgrass which comprises applying to the soil medium containing vegetative propagules thereof a toxic concentration of a compound of the formula V Y where R is trifluoromethyl, X and Y individually are lower alkyl or allyl or taken together with the nitrogen are l-pyrrolidinyl, dimethyl-l-pyrrolidinyl, l-piperidinyl or dimethyl-l-piperidinyl. I

where R is trifluoromethyl, X and Y individually are lower alkyl or allyl or taken together with the nitrogen are l-pyrrolidinyl, dimethyl-l-pyrrolidinyl, l-piperidinyl or dimethyl-l-piperidinyl.

9. The method for the selective control of nutsedge in crop plants which comprises applying to the soil medium of the crop a concentration toxic to nutsedge but substantially innocuous to the crop of a compound of the formula R if where R is trifiuoromethyl, X and Y individually are lower alkyl or allyl or taken together with the nitrogen are lpyrrolidinyl, dimethyl-l-pyrrolidinyl, l-piperidinyl or dimethyl-l-piperidinyl.

10. Herbicidal composition comprising an inert herbicidal adjuvant as carrier, a surface active agent and a 3 phytotoxic concentration of a compound of the formula where R is trifluoromethyl, X and Y individually are lower alkyl or allyl or taken together with the nitrogen are l-pyrrolidinyl, dimethyl-l-pyrrolidinyl, l-piperidinyl or dimethyl-l-piperidinyl.

11. A composition of claim 10 where X and Y are alkyl of 2 or 3 carbon atoms.

12. The method of claim 3 wherein the crop plant is corn.

13. The method of claim 3 wherein the sugar beets.

14. The method of claim 3 wherein the soybeans.

15. The method of claim 3 wherein the alfalfa.

16. The method of claim 3 wherein the wheat.

17. The method of claim 9 wherein the corn.

18. The method of claim 9 wherein the soybeans.

19. The method of claim 9 wherein the sugar beets.

crop plant is crop plant is crop plant is crop plant is crop plant is crop plant is crop plant is References Cited UNITED STATES PATENTS 2,992,091 7/1961 Harman et a1 71100 3,078,153 2/1963 Harman et al. 7l101 FOREIGN PATENTS 916,568 1/1963 Great Britain 7l100 LEWIS GOTTS, Primary Examiner G. HOLLRAH, Assistant Examiner US. Cl. X.R. 

